1. Field of the Invention
The present invention is directed to new cyclopropane compounds, their use in pest control and to pest control formulations containing the new cyclopropanecarboxylates.
2. Summary of the Invention
The present invention relates to new cyclopropane compounds of the formula ##STR2## wherein R.sup.1 is an alkyl group containing from 1 to 10 carbon atoms optionally substituted by one or more halogen atoms; a (cycloalkyl)alkyl group containing from 3 to 7 ring carbon atoms, a total of from 4 to 9 carbon atoms and optionally ring-substituted by one or more halogen atoms; a cycloalkyl group containing from 3 to 7 ring carbon atoms; an alkenyl group containing from 2 to 4 carbon atoms optionally substituted by one or more halogen atoms; an alkynyl group containing from 2 to 4 carbon atoms or an aryl group containing from 6 to 12 carbon atoms or an aralkyl group containing from 7 to 10 carbon atoms, each optionally ring-substituted by one or more halogen atoms; W is a chlorine or bromine atom or --OR in which R is a hydrogen atom, a salt-forming cation, an alkyl group containing from 1 to 20 carbon atoms or a group of the formula ##STR3## wherein Y represents hydrogen or an alkyl, alkenyl or alkynyl group or an aryl or furyl group which is unsubstituted or substituted in the ring by one or more alkyl, alkenyl, alkoxy or halogeno groups, R.sup.7 and R.sup.8, which may be the same or different, each represent hydrogen or an alkyl or alkenyl group, R.sup.9 represents hydrogen or a methyl group, R.sup.10 and R.sup.11 represent hydrogen or an alkyl group, R.sup.12 represents an organic radical having carbon-carbon unsaturation in a position .alpha. to the CH.sub.2 group to which R.sup.12 is attached, A/S indicates an aromatic ring or a dihydro or tetrahydro analogue thereof, X.sup.1, X.sup.2, X.sup.3 and X.sup.4, which may be the same or different, each represents hydrogen, halogen or a methyl group, D represents H, --CN, --C.tbd.CH or ##STR4## in which R.sup.13 and R.sup.14 may be the same or different, each represent a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, Z represents --CH.sub.2 --, --O--, --CO-- or --S--, Z.sup.1 and Z.sup.2, which may be the same or different, each represent halogen or an alkyl group containing 1 to 4 carbon atoms and n is 0, 1 or 2, R.sup.3 and R.sup.4 each independently is a hydrogen atom, a halogen atom having an atomic number of from 9 to 35, inclusive, an alkyl group containing from 1 to 4 carbon atoms or a nitro group, R.sup.5 is a hydrogen atom or a halogen atom, each R.sup.6 is a halogen atom having an atomic number of from 9 to 35, inclusive, each X.sup.5 is independently a halogen atom and m is an integer of from 1 to 5, with the proviso that when D is --CN, --C.tbd.CH or ##STR5## then the alcohol moiety is in the R,S-racemic or in the S-optical configuration.
In the above formulas, suitable halogen atoms substituents are chlorine, fluorine or bromine.
The cyclopropane compounds exhibit geometrical and optical isomerism by virtue of the double bond and the two asymmetric centers in the cyclopropane ring. Consequently, the compounds can be prepared in optically active forms, which can subsequently be mixed together, or as racemic mixtures, which can subsequently be prepared as optically active forms. Because they usually provide the highest degree of pest control, the (1R,cis) esters are preferred although the (1R,trans) esters are also active. In the esters of .alpha.-substituted alcohols in which D in formulas I, IV or VII is other than hydrogen, there is a further possibility of optical isomerism, i.e., as R or as S optical configuration; the former are without practical pest control activity. In addition, optically active forms can be separated into the individual geometrical isomers.
Examples of species within the scope of the present invention include:
.alpha.-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(2-(isobutoxyimino)-propyl)cyclopropanecarboxylate, PA0 5-benzyl-3-furylmethyl 2,2-dimethyl-3-(2-(neopentoxyimino)-propyl)cyclopropanecarboxylate, PA0 .alpha.-ethynyl-3-phenoxybenzyl 2,2-dimethyl-3-(2-(cyclopropylmethoxyimino)propyl)cyclopropanecarboxylate, PA0 .alpha.-thiocarbamoyl-3-phenoxybenzyl 2,2-dimethyl-3-(2-(propargyloxyimino)propyl)cyclopropanecarboxylate. PA0 3-benzylbenzyl 2,2-dimethyl-3-(2-(trichloroethoxyimino)-propyl)cyclopropanecarboxylate and PA0 3-phenylthiobenzyl 2,2-dimethyl-3-(2-(p-chlorophenoxyimino)-propyl)cyclopropanecarboxylates.
Matsui et al., Agr. Biol. Chem., 29, No. 8, p. 784-786, (1965) discloses the preparation of 2,2-dimethyl-3-(2-oxopropyl)cyclopropanecarboxylic acid of formula X ##STR6## from .DELTA..sup.3 -carene.
Treatment of an aqueous, preferably buffered, solution of this acid with hydroxylamine or a hydrocarbyloxyamine of the formula R.sup.1 NHOH or an acid addition salt thereof yields the corresponding novel oxyimino-substituted acid of the invention wherein W is OH.
The alcohols of the groups of formulas I through IX, inclusive, are known in the art, as for example in Elliott et al., U.S. Pat. Nos. 3,567,740 and 3,922,269 or Belgian Pat. Nos. 839,360 and 862,109. The pest control esters of the present invention can be prepared by esterification involving the reaction of an alcohol or derivative thereof of formula RQ, e.g., of formula XI, and a cyclopropanecarboxylic acid or derivative of formula XII ##STR7## wherein Q and COP are functional groups or atoms which will react to form an ester linkage and R.sup.1, D, Z, Z.sup.1 and Z.sup.2 are defined above.
It is usually convenient in practice either to treat the acid or acid halide with the alcohol (COP.dbd.COOH or CO-halide and Q.dbd.OH) or to treat a halogeno compound (Q.dbd.halogen) with a salt of the carboxylic acid (COP-COO-M) where M is, for example, a silver or ammonium cation.
Suitable routes to the esters in which D is ##STR8## are similar to those described in Belgian patent 839,360. One route involves treating the corresponding nitrile (D is --CN) with hydrogen sulfide in the presence of a basic catalyst, preferably in the presence of a solvent. Useful solvents are lower alkanols, pyridine, or preferably a dipolar aprotic solvent such as dimethylformamide or hexamethylphosphoramide. The catalyst is preferably a strong nitrogeneous base, particularly a tertiary amine such as triethylamine, trimethylamine, or the like, or an alkanolamine, such as triethanolamine, and the like. The reaction can be carried out at room temperature. It is desirable that the reaction solution be saturated with hydrogen sulfide.
Alcohols of formula RQ where R is a group of formula IV may be prepared by reduction of the corresponding acids, esters or aldehydes, e.g., with hydride, or by conversion of the corresponding halide to an ester, e.g., by reaction with sodium acetate, followed by hydrolysis of the ester, or by reaction with formaldehyde of a Gringard reagent derived from the corresponding halide. The halides of formulas RQ where R is a group of formula IV can be prepared by halomethylation of the compound ##STR9## or side chain halogenation of ##STR10##
As stated earlier, the esters wherein W is OR in which R is a group of formula I-IX are useful pest control agents having the ability to knock down insects, such as houseflies, or repel mites and/or to kill insects or mites. The particular mode of pest control activity (high knockdown, repelling or killing action) can vary with the individual cyclopropanecarboxylate ester of the invention and thus depends on the specific combination of acid and alcohol moieties.